Water-based acrylic resin for epoxy-modified glass baking finish and preparation method thereof

Abstract

The application discloses an epoxy-modified water-based acrylic resin for glass baking paint and a preparation method thereof, which is prepared from the following raw materials in mass percentage: 15-25% of methyl methacrylate, 5-10% of hydroxyethyl methacrylate, 5-15% of butyl acrylate, 5-10% of lauryl methacrylate, 5-10% of oxazolidine ethyl acrylate, 2-10% of acrylic acid, 1-5% of epoxy resin, 0.1-3% of an initiator, 10-30% of n-butanol and 5-15% of ethylene glycol butyl ether. The optimal raw material composition and ratio are obtained through a large number of experiments, and the optimal synthesis process is obtained through a large number of experiments, and the conversion rate of the application reaches 99%. The acrylic resin has excellent adhesion and solvent resistance, meanwhile, the coating film has the advantages of high hardness, good flexibility, high gloss and the like, and good technical effects are achieved in the comprehensive performance.

Description

Technical Field

[0001] This invention relates to an epoxy-modified glass baking paint waterborne acrylic resin, specifically to an epoxy-modified glass baking paint waterborne acrylic resin and its preparation method, which has high adhesion, good solvent resistance, high hardness, good flexibility, high gloss, and is easy to promote and apply, belonging to the field of polymer resin technology. Background Technology

[0002] Acrylic resins possess characteristics such as good transparency, glossy color, corrosion resistance, high hardness, and good toughness, making them widely used in coating materials. However, under certain conditions, the use of ordinary acrylic resins exhibits certain performance defects, primarily poor adhesion to some material surfaces, solvent resistance, and mechanical properties, thus hindering the development and application of acrylic resins. Summary of the Invention

[0003] Purpose of the invention: The purpose of this invention is to address the shortcomings of existing technologies by introducing epoxy resin into acrylic resin for modification. The optimal composition of acrylic resin monomers and initiators is selected and adjusted. At the same time, special acrylic monomers lauryl methacrylate and oxazolidine ethyl acrylate are added to prepare a waterborne acrylic resin with excellent comprehensive properties such as high adhesion, good solvent resistance, good flexibility, high transparency, and high hardness.

[0004] Technical solution: To achieve the above objectives, the technical solution adopted by this invention is as follows:

[0005] An epoxy-modified glass baking paint waterborne acrylic resin is made from the following raw materials: methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine acrylate, acrylic acid, epoxy resin, initiator, n-butanol and ethylene glycol butyl ether.

[0006] As a preferred embodiment, the epoxy-modified glass paint described above uses a water-based acrylic resin, which is made from the following raw materials in the following mass percentages: 15-25% methyl methacrylate, 5-10% hydroxyethyl methacrylate, 5-15% butyl acrylate, 5-10% lauryl methacrylate, 5-10% oxazolidine acrylate, 2-10% acrylic acid, 1-5% epoxy resin, 0.1-3% initiator, 10-30% n-butanol, and 5-15% ethylene glycol butyl ether.

[0007] As a preferred embodiment, the epoxy-modified glass paint described above uses a water-based acrylic resin, with tert-butyl peroxide as the initiator.

[0008] As a preferred embodiment, the epoxy-modified glass coating described above uses a water-based acrylic resin, wherein the epoxy resin is epoxy resin 601 produced by Jiangsu Sanmu Chemical Co., Ltd.

[0009] As a preferred embodiment, the epoxy-modified glass paint described above uses a water-based acrylic resin, wherein the special acrylate monomers added to the resin are lauryl methacrylate and oxazolidine ethyl acrylate.

[0010] As a preferred embodiment, the epoxy-modified glass coating described above uses a water-based acrylic resin, wherein the solvent of the resin is n-butanol and ethylene glycol butyl ether.

[0011] The present invention discloses a method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin, comprising the following steps:

[0012] (1) Add epoxy resin, n-butanol and ethylene glycol butyl ether mixture to the reaction apparatus and heat to 120-125℃;

[0013] (2) Mix methyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, lauryl methacrylate, oxazolidine acrylate, acrylic acid, and initiator evenly and add them to a dropping funnel.

[0014] (3) When the temperature of the reaction apparatus in step (1) reaches 120-125°C, start adding the mixture in step (2) dropwise. The dropwise addition is completed in 3.5-4 hours. After the dropwise addition is completed, keep the temperature for 1.5-2 hours. Then add the first part of the initiator and keep the temperature for 0.5-1 hour again. Then add the second part of the initiator and keep the temperature for 0.5-1 hour again to obtain the final product.

[0015] As a preferred embodiment, the epoxy-modified glass coating described above uses a water-based acrylic resin, with tert-butylbenzoyl peroxide as the initiator.

[0016] As a preferred embodiment, the epoxy-modified glass coating described above uses a water-based acrylic resin, wherein the epoxy resin is epoxy resin 601.

[0017] As a preferred embodiment, a method for preparing waterborne acrylic resin for epoxy-modified glass baking paint is characterized in that, in step (3), when the temperature of the reaction device in step (1) reaches 120-125℃, the mixture in step (2) is added dropwise, and the addition is completed in 4 hours. After the addition is completed, the mixture is kept warm for 2 hours. Then, the first part of the initiator is added, and the mixture is kept warm for 1 hour again. Then, the second part of the initiator is added, and the mixture is kept warm for 1 hour again, thus obtaining the product.

[0018] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0019] This invention, through extensive experimental screening, introduces epoxy resin into an acrylic resin system. Simultaneously, it optimizes and adjusts the composition of the acrylic resin monomers, special acrylic monomers, and initiator system. The epoxy resin selected in this invention is epoxy resin 601. The acrylic resin synthesized from lauryl methacrylate and oxazolidine acrylate not only possesses advantages such as high adhesion, good solvent resistance, and good flexibility, but also exhibits excellent comprehensive properties such as high transparency and high hardness. Furthermore, the initiator used is tert-butyl peroxide (2-ethylhexanoate). At a relatively high reaction temperature of 125°C, through a longer dropping time and the method of adding two parts of initiator followed by a second heat treatment, the resin achieves a high conversion rate, reaching 99%. The acrylic resin prepared by this invention possesses advantages such as high adhesion, good solvent resistance, and good flexibility, while also exhibiting excellent comprehensive properties such as high transparency and high hardness. Detailed Implementation

[0020] Example 1

[0021] 1. An epoxy-modified glass baking paint waterborne acrylic resin, which is made from the following raw materials in the following weight percentages: 20% methyl methacrylate, 7% hydroxyethyl methacrylate, 6% butyl acrylate, 8% lauryl methacrylate, 9% oxazolidine acrylate, 5% acrylic acid, 3% epoxy resin, 2% initiator, 27% n-butanol and 13% ethylene glycol butyl ether.

[0022] 2. The preparation method of the epoxy-modified glass baking paint using water-based acrylic resin according to the present invention includes the following steps:

[0023] (1) Add 30g of epoxy resin 601 (produced by Jiangsu Sanmu Chemical Co., Ltd., the same below), 130g of ethylene glycol butyl ether and 270g of n-butanol to the reaction apparatus, start stirring and heat to 120-125℃.

[0024] (2) Mix 200g of methyl methacrylate, 70g of hydroxyethyl methacrylate, 60g of butyl acrylate, 80g of lauryl methacrylate, 90g of oxazolidine acrylate, 50g of acrylic acid, and 16g of tert-butyl peroxide with a measured amount of methyl methacrylate, and then add the mixture to a dropping funnel.

[0025] (3) When the temperature of the reaction device in step (1) reaches 120-125℃, the mixed monomer and initiator in step (2) are added dropwise over 4 hours. After the addition is complete, the temperature is maintained for 2 hours. Then, 2 grams of tert-butyl peroxide (TBPO) are added and the temperature is maintained for 1 hour. Then, 2 grams of tert-butyl peroxide (TBPO) are added again and the temperature is maintained for 1 hour before the product is discharged. The final conversion rate of the reaction can reach 99%, and the resin solid content is 59.5%.

[0026] Comparative Example 1

[0027] A method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin includes the following steps:

[0028] (1) Add 130 g of ethylene glycol butyl ether and 270 g of n-butanol to the reaction apparatus, start stirring and heat to 120-125℃;

[0029] (2) Mix 200g of methyl methacrylate, 70g of hydroxyethyl methacrylate, 90g of butyl acrylate, 80g of lauryl methacrylate, 90g of oxazolidine acrylate, 50g of acrylic acid, and 16g of tert-butyl peroxide with a measured amount of methyl methacrylate and add the mixture to a dropping funnel.

[0030] (3) When the temperature of the reaction device in step (1) reaches 120-125℃, the mixed monomer and initiator in step (2) are added dropwise. The addition is completed in 4 hours. After the addition is completed, the temperature is maintained for 2 hours. Then, 2 grams of tert-butyl peroxide (TBPO) are added and the temperature is maintained for 1 hour. Then, 2 grams of tert-butyl peroxide (TBPO) are added again and the temperature is maintained for 1 hour. The product is then discharged. The final conversion rate of the reaction can reach 98%, and the resin solid content is 59%.

[0031] Comparative Example 2

[0032] A method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin includes the following steps:

[0033] (1) Add 30g of epoxy resin 601, 130g of ethylene glycol butyl ether and 270g of n-butanol to the reaction apparatus, start stirring and heat to 120-125℃.

[0034] (2) Mix 240g of methyl methacrylate, 70g of hydroxyethyl methacrylate, 100g of butyl acrylate, 90g of oxazolidinyl acrylate, 50g of acrylic acid, and 16g of tert-butyl peroxide with a measured amount of methyl methacrylate and add the mixture to a dropping funnel.

[0035] (3) When the temperature of the reaction apparatus in step (1) reaches 120-125℃, the mixed monomer and initiator in step (2) are added dropwise over 4 hours. After the addition is complete, the mixture is kept warm for 2 hours. Then, 2 grams of tert-butyl peroxide (TBPO) are added and kept warm for 1 hour. Then, 2 grams of tert-butyl peroxide (TBPO) are added again and kept warm for 1 hour before the mixture is discharged. The final conversion rate of the reaction can reach 98%, and the resin solid content is 58.9%.

[0036] Comparative Example 3

[0037] A method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin includes the following steps:

[0038] (1) Add 30g of epoxy resin 601, 130g of ethylene glycol butyl ether and 270g of n-butanol to the reaction apparatus, start stirring and heat to 120-125℃.

[0039] (2) Mix 250g of methyl methacrylate, 70g of hydroxyethyl methacrylate, 100g of butyl acrylate, 80g of lauryl methacrylate, 50g of acrylic acid, and 16g of tert-butyl peroxide evenly, and then add the mixture to a dropping funnel.

[0040] (3) When the temperature of the reaction device in step (1) reaches 120-125℃, the mixed monomer and initiator in step (2) are added dropwise over 4 hours. After the addition is complete, the temperature is maintained for 2 hours. Then, 2 grams of tert-butyl peroxide (TBPO) are added and the temperature is maintained for 1 hour. Then, 2 grams of tert-butyl peroxide (TBPO) are added again and the temperature is maintained for 1 hour before the product is discharged. The final conversion rate of the reaction can reach 98%, and the resin solid content is 58.8%.

[0041] Comparative Example 4

[0042] A method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin includes the following steps:

[0043] (1) Add 30g of epoxy resin 601, 130g of ethylene glycol butyl ether and 270g of n-butanol to the reaction apparatus, start stirring and heat to 120-125℃.

[0044] (2) Mix 200g of methyl methacrylate, 70g of hydroxyethyl methacrylate, 60g of butyl acrylate, 80g of lauryl methacrylate, 90g of oxazolidine acrylate, 50g of acrylic acid, and 16g of tert-butyl peroxide with a measured amount of methyl methacrylate, and then add the mixture to a dropping funnel.

[0045] (3) When the temperature of the reaction apparatus in step (1) reaches 120-125℃, the mixed monomers and initiator from step (2) are added dropwise over 4 hours. After the addition is complete, the mixture is kept at this temperature for 2 hours. Then, 2 grams of benzoyl peroxide (BPO) are added, and the mixture is kept at this temperature for 1 hour. After adding another 2 grams of benzoyl peroxide (BPO) and keeping the mixture at this temperature for 1 hour, the product is discharged. The final conversion rate of the reaction is only 92%, and the resin solid content is 55.2%.

[0046] Application Example 1

[0047] 1. The acrylic resins prepared in Example 1 and Comparative Examples 1, 2, 3 and 4 above are formulated into baking paint according to the formula in Table 1 below.

[0048] Table 1. Composition of Acrylic Resin Waterborne Glass Paint Formulation

[0049]

[0050]

[0051] Add 20% dilution and spray, then bake at 170℃ for 20 minutes.

[0052] 2. Paint film inspection

[0053] The baking paints prepared from the acrylic resins of Example 1 and Comparative Examples 1, 2, 3 and 4 were subjected to the following tests:

[0054] Among them, hardness (pencil scratch) was determined according to GB / T6739-1996 Test of Pencil Hardness of Coating; impact (recoil) was determined according to GB / T1732-93 Test of Impact Resistance of Coating; adhesion (circle scratch method) was determined according to GB / T1720-79(89) Test of Adhesion of Coating; the specific test results of clear varnish are shown in Tables 2 and 3:

[0055] Table 2 Results of mechanical properties and contact angle tests of the coating film

[0056]

[0057] The above experimental results demonstrate that this invention, through extensive experimentation and screening of various reactive raw material compositions, particularly the formulation of epoxy resin 601, lauryl methacrylate, and oxazolidine ethyl acrylate, produces an epoxy-modified glass baking varnish using water-based acrylic resin. This resin not only possesses advantages such as high adhesion, good solvent resistance, and good flexibility, but also exhibits excellent comprehensive properties including high transparency and high hardness. This overcomes the shortcomings of existing technologies and achieves unexpected and significant technical results.

[0058] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A water-based acrylic resin for epoxy-modified glass baking paint, characterized in that, It is made from the following raw materials in the following weight percentages: 15-25% methyl methacrylate, 5-10% hydroxyethyl methacrylate, 5-15% butyl acrylate, 5-10% lauryl methacrylate, 5-10% oxazolidine acrylate, 2-10% acrylic acid, 1-5% epoxy resin, 0.1-3% initiator, 10-30% n-butanol and 5-15% ethylene glycol butyl ether; The initiator is tert-butyl peroxide-2-ethylhexanoate.

2. The waterborne acrylic resin for epoxy-modified glass baking paint according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 20% methyl methacrylate, 7% hydroxyethyl methacrylate, 6% butyl acrylate, 8% lauryl methacrylate, 9% oxazolidinyl acrylate, 5% acrylic acid, 3% epoxy resin, 2% initiator, 27% n-butanol and 13% ethylene glycol butyl ether.

3. The method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin as described in claim 1 or 2, characterized in that, Includes the following steps: (1) Add epoxy resin, n-butanol and ethylene glycol butyl ether mixture to the reaction apparatus and heat to 110-130℃; (2) Mix methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine acrylate, acrylic acid, and initiator evenly, and then add them to a dropping funnel. (3) When the temperature of the reaction apparatus in step (1) reaches 110~130℃, start adding the mixture in step (2). After the addition is complete, keep it warm for a period of time, then add the first part of the initiator, keep it warm for a period of time again, then add the second part of the initiator, keep it warm for a period of time again, and so on.

4. The method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin according to claim 3, characterized in that, Includes the following steps: (1) Add epoxy resin, n-butanol and ethylene glycol butyl ether mixture to the reaction apparatus and heat to 120-130℃; (2) Mix methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine acrylate, acrylic acid, and initiator evenly, and then add them to a dropping funnel. (3) When the temperature of the reaction apparatus in step (1) reaches 120~130℃, start adding the mixture in step (2) dropwise. The dropwise addition is completed in 1~4 hours. After the dropwise addition is completed, keep the temperature for 0.5~2 hours. Then add the first part of the initiator and keep the temperature for 0.5~1.5 hours again. Then add the second part of the initiator and keep the temperature for 0.5~1.5 hours again to obtain the final product.

5. The method for preparing an epoxy-modified glass baking varnish using a water-based acrylic resin according to claim 4, characterized in that, In step (3), when the temperature of the reaction apparatus in step (1) reaches 120~125℃, the mixture in step (2) is added dropwise. The addition is completed in 4 hours. After the addition is completed, the mixture is kept warm for 2 hours. Then, the first part of the initiator is added, and the mixture is kept warm for 1 hour again. Then, the second part of the initiator is added, and the mixture is kept warm for 1 hour again. The mixture is then obtained.

6. The application of the epoxy-modified glass baking paint as described in claim 1 or 2 in the preparation of glass baking paint film.

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